Oil-based suspension concentrates

ABSTRACT

This invention relates to new oil-based suspension concentrates containing  
     at least one agrochemical active compound which is solid at room temperature,  
     at least one penetration promoter,  
     at least one vegetable oil,  
     one or more non-ionic surfactants or dispersing aids and/or one or more anionic surfactants or dispersing aids and  
     optionally one or more additives selected from the group consisting of emulsifying agents, antifoam agents, preservatives, antioxidants, colorants and/or inert filling materials,  
     to a process for the preparation of these suspension concentrates and to their use for the application of the active compounds contained therein.

[0001] The present invention relates to new, oil-based suspensionconcentrates of agrochemical active compounds, a process for thepreparation of these formulations and their use for the application ofthe active compounds contained.

[0002] Numerous anhydrous suspension concentrates of agrochemical activecompounds have already been disclosed. Thus, EP-A 0 789 999 describesformulations of this type which, in addition to active compound and oil,contain a mixture of various surfactants, —among them also those whichserve as penetration promoters—, and a hydrophobized alumo-layersilicate as a thickening agent. The stability of these preparations isgood. It is disadvantageous, however, that a thickening agent iscompulsorily present, because the preparation is more complicated onaccount of this. Moreover, the thickening agent in each case absorbssome of the amount of penetration promoter added, which is therefore notavailable for its real function.

[0003] Furthermore, U.S. Pat. No. 6,165,940 already disclosesnon-aqueous suspension concentrates in which, apart from agrochemicalactive compound, penetration promoter and surfactant or surfactantmixture, an organic solvent is present, suitable solvents of this typealso being paraffin oil or vegetable oil esters. The biological activityand the stability of the spray liquors which can be prepared from theseformulations by diluting with water, however, is not always adequate.

[0004] New oil-based suspension concentrates have now been found, whichconsist of

[0005] at least one agrochemical active compound which is solid at roomtemperature,

[0006] at least one penetration promoter,

[0007] at least one vegetable oil,

[0008] at least one non-ionic surfactant or dispersing aid and/or atleast one anionic surfactant or dispersing aid and

[0009] optionally one or more additives from the group consisting of theemulsifying agents, the antifoam agents, the preservatives, theantioxidants, the colourants and/or the inert filling materials.

[0010] It has furthermore been found that the oil-based suspensionconcentrates according to the invention can be prepared by mixing

[0011] at least one agrochemical active compound which is solid at roomtemperature,

[0012] at least one penetration promoter,

[0013] at least one vegetable oil,

[0014] at least one non-ionic surfactant or dispersing aid and/or atleast one anionic surfactant or dispersing aid and

[0015] optionally one or more additives from the groups consisting ofthe emulsifying agents, the antifoam agents, the preservatives, theantioxidants, the colourants and/or the inert filling materials

[0016] with one another and then optionally grinding the resultingsuspension.

[0017] Finally, it has been found that the oil-based suspensionconcentrates according to the invention are very highly suitable for theapplication of the agrochemical active compounds contained to plantsand/or their habitat.

[0018] It is to be indicated as extremely surprising that the oil-basedsuspension concentrates according to the invention have a very goodstability, although they contain no thickening agent. It is alsounexpected that they exhibit a markedly better biological activity thanthe previously known formulations having the most similar composition.Otherwise, the oil-based suspension concentrates according to theinvention, with respect to their activity, surprisingly also excelanalogous preparations which, in addition to the other components,contain either only penetration promoter or only vegetable oil. Such asynergistic effect could not be foreseen on the basis of the prior artdescribed above.

[0019] The oil-based suspension concentrates according to the inventionare also distinguished by a number of advantages. Thus their preparationis less complicated than the preparation of corresponding formulationsin which thickening agents are present. It is furthermore advantageousthat on diluting the concentrates according to the invention with waterneither a significant formation of cream nor a troublesome formation offlocks occurs, which is frequently the case with correspondingpreviously known preparations. Finally, the formulations according tothe invention favour the biological activity of the active componentscontained, so that in comparison to conventional preparations either ahigher activity is achieved or less active compound is necessary.

[0020] Solid, agrochemical active compounds are to be understood in thepresent composition as meaning all substances customary for planttreatment, whose melting point is above 20° C. Fungicides, bactericides,insecticides, acaricides, nematicides, molluscicides, herbicides, plantgrowth regulators, plant nutrients and repellents may preferably bementioned.

[0021] Examples of fungicides which may be mentioned are:

[0022] 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoro-methoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoro-methylbenzyl)-benzamide;(E)-2-methoximino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]-acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

[0023] benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

[0024] calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram, carpropamide,

[0025] dichlorophen, diclobutrazole, dichlofluanid, diclomezin,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos,dithianon, dodine, drazoxolon,

[0026] edifenphos, epoxyconazole, ethirimol, etridiazole,

[0027] fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam,fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide,flutolanil, flutriafol, folpet, fosetyl-aluminium, fthalide,fuberidazole, furalaxyl, firmecyclox, fenhexamide,

[0028] guazatine,

[0029] hexachlorobenzene, hexaconazole, hymexazole,

[0030] imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),iprodion, isoprothiolan, iprovalicarb,

[0031] kasugamycin, copper preparations, such as: copper hydroxide,copper naphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture,

[0032] mancopper, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl,metconazole, methasulfocarb, methfuroxam, metiram, metsulfovax,myclobutanil,

[0033] nickel dimethyldithiocarbarnate, nitrothal-isopropyl, nuarimol,

[0034] ofurace, oxadixyl, oxamocarb, oxycarboxine,

[0035] pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin,piperalin, polyoxine, probenazole, prochloraz, procymidon, propamocarb,propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil,pyroquilon,

[0036] quintozene (PCNB), quinoxyfen,

[0037] sulphur and sulphur preparations,

[0038] tebuconazole, tecloftalam, tecnazene, tetraconazole,thiabendazole, thicyofen, thiophanate-methyl, thiram, toldlophos-methyl,tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide,tricyclazole, tridemorph, triflumizole, triforin, triticonazole,trifloxystrobin,

[0039] validamycin A, vinclozolin,

[0040] zineb, ziram and

[0041]2-[2-(1-chloro-cyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione.

[0042] Examples of bactericides which may be mentioned are:

[0043] bronopol, dichlorophen, nitrapyrin, nickeldimethyldithiocarbamate, kasugamycin, octhilinon, furancarboxylic acid,oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphateand other copper preparations.

[0044] Examples of insecticides, acaricides and nematicides which may bementioned are:

[0045] abamectin, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin,

[0046]Bacillus thuringiensis,4-bromo-2-(4-chlorphenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxine,butylpyridaben,

[0047] cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,cartap, chloethocarb, chloretoxyfos, chlorfenvinphos, chlorfluazuron,chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethaneimidamide,chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin,cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazin,

[0048] deltamethrin, demeton-M, demeton-S, demeton-S-methyl,diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,dicrotophos, diethion, diflubenzuron, dimethoate,

[0049] dimethylvinphos, dioxathion, disulfoton,

[0050] emamectin, esfen valerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos,

[0051] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,fenpyroximate, fenthion, fenvalerate, fipronil, fluazuron,flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,fonophos, formothion, fosthiazate, fubfenprox, furathiocarb,

[0052] HCH, heptenophos, hexaflumuron, hexythiazox,

[0053] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,isoxathion, ivermectin, lambda-cyhalothrin, lufenuron,

[0054] malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde,methacrifos, methamidophos, methidathion, methiocarb, methomyl,metolcarb, milbemectin, monocrotophos, moxidectin,

[0055] naled, NC 184, nitenpyram,

[0056] omethoate, oxamyl, oxydemethon M, oxydeprofos,

[0057] parathion A, parathion M, permethrin, phenthoate, phorate,phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenophos, promecarb, propaphos, propoxur, prothiophos,prothoate, pymetrozine, pyrachlophos, pyridaphenthion, pyresmethrin,pyrethrum, pyridaben, pyrimidifen, pyriproxifen,

[0058] quinalphos,

[0059] salithion, sebufos, silafluofen, sulfotep, sulprofos,

[0060] tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron,tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiacloprid,thiafenox, thiamethoxam, thiodicarb, thiofanox, thiomethon, thionazine,thuringiensin, tralomethrin, transfluthrin, triarathen, triazophos,triazuron, trichlorfon, triflumuron, trimethacarb,

[0061] vamidothion, XMC, xylylcarb, zetamethrin.

[0062] Examples of molluscicides which may be mentioned are metaldehydeand methiocarb.

[0063] Examples of herbicides which may be mentioned are:

[0064] anilides, such as, for example, diflufenican and propanil;arylcarboxylic acids, such as, for example, dichlorpicolinic acid,dicamba and picloram; aryloxyalkanoic acids, such as, for example,2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoic acid esters, such as, for example,diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones, such as, for example, chloridazon andnorflurazon; carbamates, such as, for example, chlorpropham,desmedipham, phenmedipham and propham; chloroacetanilides, such as, forexample, alachlor, acetochlor, butachlor, metazachlor, metolachlor,pretilachlor and propachlor; dinitroarilines, such as, for example,oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as, forexample, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen,lactofen and oxyfluorfen; ureas, such as, for example, chlortoluron,diuron, fluometuron, isoproturon, linuron and methabenzthiazuron;hydroxylamines, such as, for example, alloxydim, clethodim, cycloxydim,sethoxydim and tralkoxydim; imidazolinones, such as, for example,imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as,for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides, suchas, for example, mefenacet; sulphonylureas, such as, for example,amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron,pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron andtribenuron-methyl; thiocarbamates, such as, for example, butylate,cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarband triallate; triazines, such as, for example, atrazine, cyanazine,simazine, simetryne, terbutryne and terbutylazine; triazinones, such as,for example, hexazinon, metamitron and metribuzin; others, such as, forexample, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone,clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone,glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac,sulphosate and tridiphane. In addition,4-amino-N-(1,1-dimethylethyl)-4,5-dihydro-3-(1-methylethyl)-5-oxo-1H-1,2,4-triazole-1-carboxamideand2-((((4,5-dihdydro-4-methyl-5-oxo-3-propoxy-1H-1,2,4-triazol-1-yl)carbonyl)amino)sulfonyl)methyl benzoate may be mentioned.

[0065] Examples of plant growth regulators which may be mentioned arechlorocholine chloride and ethephon.

[0066] Examples of plant nutrients which may be mentioned are customaryinorganic or organic fertilizers for supplying plants with macro- and/ormicronutrients.

[0067] Examples of repellents which may be mentioned arediethyl-tolylamide, ethylhexane-diol and buto-pyronoxyl.

[0068] Suitable penetration promoters in the present composition are allthose substances which are customarily employed in order to improve thepenetration of agrochemical active compounds into plants. Alkanolalkoxylates of the formula

R—O-(-AO)_(m)H   (I)

[0069] in which

[0070] R represents straight-chain or branched alkyl having 4 to 20carbon atoms,

[0071] AO represents an ethylene oxide radical, a propylene oxideradical, a butylene oxide radical, or mixtures of ethylene oxide andpropylene oxide radicals or butylene oxide radicals and

[0072] m represents numbers from 2 to 30,

[0073] are preferred.

[0074] A particularly preferred group of penetration promoters arealkanol alkoxylates of the formula

R—O-(-EO—)_(n)—H   (Ia)

[0075] in which

[0076] R has the meaning indicated above,

[0077] EO represents —CH₂—CH₂—O— and

[0078] n represents numbers from 2 to 20.

[0079] A further particularly preferred group of penetration promotersare alkanol alkoxylates of the formula

R—O-(-EO—)_(p)—(—PO—)_(q)—H   (Ib)

[0080] in which

[0081] R has the meaning indicated above,

[0082] EO represents —CH₂—CH₂—O—,

[0083] PO represents

[0084] p represents numbers from 1 to 10 and

[0085] q represents numbers from 1 to 10.

[0086] A further particularly preferred group of penetration promotersare alkanol alkoxylates of the formula

R—O—(—PO—)_(r)-(EO—)_(s)—H   (Ic)

[0087] in which

[0088] R has the meaning indicated above,

[0089] EO represents —CH₂—CH₂—O—,

[0090] PO represents

[0091] r represents numbers from 1 to 10 and

[0092] s represents numbers from 1 to 10.

[0093] A further particularly preferred group of penetration promotersare alkanol alkoxylates of the formula

CH₃—(CH₂)_(t)—CH₂—O—(—CH₂—CH₂—O—)_(u)—H   (Id)

[0094] in which

[0095] t represents numbers from 8 to 13 and

[0096] u represents numbers from 6 to 17.

[0097] In the formulae indicated beforehand

[0098] R preferably represents butyl, i-butyl, n-pentyl, i-pentyl,neopentyl, n-hexyl, i-hexyl, n-octyl, i-octyl, 2-ethyl-hexyl, nonyl,i-nonyl, decyl, n-dodecyl, i-dodecyl, lauryl, myristyl, i-tridecyl,trimethyl-nonyl, palnityl, stearyl or eicosyl.

[0099] An example of an alkanol alkoxylate of the formula (1c) which maybe mentioned is 2-ethyl-hexyl alkoxylate of the formula

[0100] in which

[0101] EO represents —CH₂—CH₂—O—,

[0102] PO represents

[0103] and the numbers 8 and 6 are average values.

[0104] Particularly preferred alkanol alkoxylates of the formula (Id)are compounds of this formula in which

[0105] t represents numbers from 9 to 12 and

[0106] u represents numbers from 7 to 9.

[0107] The above formulae give a general definition of the alkanolalkoxylates. These substances are mixtures of substances of the typeindicated having different chain lengths. For the indices, therefore,average values are calculated which can also differ from integers.

[0108] By way of example, an alkanol alkoxylate of the formula (Id) maybe mentioned, in which

[0109] t represents the average value 10.5 and

[0110] u represents the average value 8.4.

[0111] The alkanol alkoxylates of the formulae indicated are known orcan be prepared by known methods (cf. WO 98-35 553, WO 00-35 278 andEP-A 0 681 865).

[0112] Possible vegetable oils are all oils which can customarily beemployed in agrochemical agents and can be obtained from plants. By wayof example, sunflower oil, rapeseed oil, olive oil, castor oil, colzaoil, maize germ oil, cottonseed oil and soya bean oil may be mentioned.

[0113] The oil-based suspension concentrates according to the inventioncontain at least one non-ionic surfactant or dispersing aid and/or atleast one anionic surfactant or dispersing aid.

[0114] Suitable non-ionic surfactants or dispersing aids are allsubstances of this type which can customarily be employed inagrochemical agents. Preferably, polyethylene oxide- polypropylene oxideblock copolymers, polyethylene glycol ethers of linear alcohols,reaction products of fatty acids with ethylene oxide and/or propyleneoxide, furthermore polyvinyl alcohol, polyvinylpyrrolidone, copolymersof polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of(meth)acrylic acid and (meth)-acrylic acid esters, furthermore alkylethoxylates and alkylaryl ethoxylates, which can be optionallyphosphated and optionally neutralized with bases, where sorbitolethoxylates may be mentioned by way of example, and polyoxyalkylenaminederivatives may be mentioned.

[0115] Possible anionic surfactants are all substances of this typewhich can customarily be employed in agrochemical agents. Alkali metaland alkaline earth metal salts of alkylsulphonic acids oralkylarylsulphonic acids are preferred.

[0116] A further preferred group of anionic surfactants or dispersingaids are salts of poly-styrenesulphonic acids, salts ofpolyvinylsulphonic acids, salts of naphthalene-sulphonicacid-formaldehyde condensation products, salts of condensation productsof naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, andsalts of lignosulphoric acid, which are not very soluble in vegetableoil.

[0117] Suitable additives which can be contained in the formulationsaccording to the invention are emulsifiers, antifoam agents,preservatives, antioxidants, colourants and inert filling materials.

[0118] Preferred emulsifiers are ethoxylated nonylphenols, reactionproducts of alkylphenols with ethylene oxide and/or propylene oxide,ethoxylated arylalkylphenols, furthermore ethoxylated and propoxylatedarylalkylphenols, and sulphated or phosphated arylalkyl ethoxylates or-ethoxy-propoxylates, where sorbitan derivatives, such as polyethyleneoxide-sorbitan fatty acid esters and sorbitan fatty acid esters, may bementioned by way of example.

[0119] Suitable antifoam substances are all substances which cancustomarily be employed in agrochemical agents for this purpose.Silicone oils and magnesium stearate are preferred.

[0120] Possible preservatives are all substances which can customarilybe employed in agrochemical agents for this purpose. Examples which maybe mentioned are Preventol® (Bayer AG) and Proxel®.

[0121] Suitable antioxidants are all substances which can customarily beemployed in agrochemical agents for this purpose. Butylhydroxytoluene ispreferred.

[0122] Possible colourants are all substances which can customarily beemployed in agrochemical agents for this purpose. Titanium dioxide,carbon black, zinc oxide and blue pigments, and Permanent Red FGR may bementioned by way of example.

[0123] Suitable inert filling materials are all substances which cancustomarily be employed in agrochemical agents for this purpose, andwhich do not function as thickening agents. Inorganic particles, such ascarbonates, silicates and oxides and also organic substances, such asurea-formaldehyde condensates, are preferred. Kaolin, rutile, silica(“highly disperse silicic acid”), silica gels, and natural and syntheticsilicates, moreover talc, may be mentioned by way of example.

[0124] The content of the individual components can be varied within awide range in the oil-based suspension concentrates according to theinvention. Thus, the concentrations

[0125] of agrochemical active compounds are in general between 5 and 30%by weight, preferably between 10 and 25% by weight,

[0126] of penetration promoter are in general between 5 and 55% byweight, preferably between 15 and 40% by weight,

[0127] of vegetable oil are in general between 15 and 55% by weight,preferably between 20 and 50% by weight,

[0128] of surfactants or dispersing aids are in general between 2.5 and30% by weight, preferably between 5.0 and 25% by weight and

[0129] of additives are in general between 0 and 25% by weight,preferably between 0 and 20% by weight.

[0130] The oil-based suspension concentrates according to the inventionare prepared by mixing the components with one another in the ratiosdesired in each case. The sequence in which the constituents are blendedwith one another is arbitrary. Expediently, the solid components areemployed in finely ground state. However, it is also possible firstly tosubject the suspension resulting after the blending of the constituentsto a coarse grinding and then to a fine grinding so that the averageparticle size is below 20 μm. Suspension concentrates are preferred inwhich the solid particles have an average particle size of between 1 and10 μm.

[0131] The temperatures can be varied within a certain range whencarrying out the process according to the invention. The process is ingeneral carried out at temperatures between 10° C. and 60° C.,preferably between 15° C. and 40° C.

[0132] For carrying out the process according to the invention,customary mixing and grinding equipment is suitable which is employedfor the preparation of agrochemical formulations.

[0133] The oil-based suspension concentrates according to the inventionare formulations which remain stable even after relatively long storageat elevated temperatures or in the cold, since no crystal growth isobserved. They can be converted into homogeneous spray liquids bydilution with water. These spray liquids are used according to customarymethods, i.e., for example, by spraying, watering or injecting.

[0134] The application rate of the oil-based suspension concentratesaccording to the invention can be varied within a relatively wide range.It depends on the particular agrochemical active compounds and on theircontent in the formulations.

[0135] With the aid of the oil-based suspension concentrates accordingto the invention, agrochemical active compounds can be applied to plantsand/or their habitat in a particularly advantageous manner. Theagrochemical active compounds contained in this case display a betterbiological activity than on application in the form of the correspondingconventional formulations.

[0136] The invention is illustrated by the following examples.

PREPARATION EXAMPLES Example 1

[0137] For the preparation of a suspension concentrate

[0138] 48.4 g of thiacloprid

[0139] 45.6 g of a mixture of alkylarylsulphonate, ethylhexanol andalkanol ethoxylate

[0140] 40.0 g of polyoxyethylene sorbitol oleate,

[0141] 0.4 g of silicone oil and

[0142] 0.8 g of butylhydroxytoluene

[0143] are added with stirring at room temperature to a mixture of

[0144] 88.0 g of 2-ethyl-hexyl alkoxylate of the formula

[0145] in which

[0146] EO represents —CH₂—CH₂—O—,

[0147] PO represents

[0148] and the numbers 5 and 3 are average values,

[0149] and

[0150] 176.8 g of sunflower oil.

[0151] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 ptm.

Example 2

[0152] For the preparation of a suspension concentrate

[0153] 78.2 g of thiacloprid

[0154] 40.0 g of a mixture of calcium alkylarylsulphonate, alkylphenolethoxylate and naphtha solution

[0155] 40.0 g of polyoxyethylene sorbitol oleate

[0156] 0.4 g of silicone oil and

[0157] 0.8 g of butylhydroxytoluene

[0158] are added with stirring at room temperature to a mixture of

[0159] 80.0 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2) and

[0160] 160.6 g of sunflower oil.

[0161] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 μm.

Example 3

[0162] For the preparation of a suspension concentrate

[0163] 50.4 g of thiacloprid

[0164] 27.5 g of a mixture of alkylarylsulphonate and ethylhexanol

[0165] 5.25 g of singly branched alkanol ethoxylate having on average 15ethylene oxide groups

[0166] 25.0 g of polyoxyethylene sorbitol oleate

[0167] 0.25 g of silicone oil and

[0168] 0.5 g of butylhydroxytoluene

[0169] are added with stirring at room temperature to a mixture of

[0170] 50.0 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2) and

[0171] 91.1 g of sunflower oil.

[0172] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 μm.

Example 4

[0173] For the preparation of a suspension concentrate

[0174] 49.4 g of thiacloprid

[0175] 23.75 g of a mixture of alkylarylsulphonate and ethylhexanol

[0176] 4.5 g of singly branched alkanol ethoxylate having on average 15ethylene oxide groups

[0177] 25.0 g of polyoxyethylene sorbitol oleate

[0178] 0.25 g of silicone oil and

[0179] 0.5 g of butylhydroxytoluene

[0180] are added with stirring at room temperature to a mixture of

[0181] 50.0 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2) and

[0182] 96.6 g of sunflower oil.

[0183] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solids particles have a particle size of below 6 μm.

Example 5

[0184] For the preparation of a suspension concentrate

[0185] 692.54 g of thiacloprid

[0186] 300.0 g of a mixture of alkylarylsulphonate, alkanol ethoxylateand naphtha solution

[0187] 300.0 g of polyoxyethylene sorbitol oleate

[0188] 3.0 g of silicone oil and

[0189] 6.0 g of butylhydroxytoluene

[0190] are added with stirring at room temperature to a mixture of

[0191] 600.0 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2) and

[0192] 1098.46 g of sunflower oil.

[0193] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 μm.

Example 6

[0194] For the preparation of a suspension concentrate

[0195] 577.1 g of thiacloprid

[0196] 327.5 g of a mixture of alkylarylsulphonate, ethylhexanol andalkanolethoxylate

[0197] 250.0 g of polyoxyethylene sorbitol oleate

[0198] 2.5 g of silicone oil and

[0199] 5.0 g of butylhydroxytoluene

[0200] are added with stirring at room temperature to a mixture of

[0201] 500.0 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2) and

[0202] 837.9 g of sunflower oil.

[0203] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 μm.

Example 7

[0204] For the preparation of a suspension concentrate

[0205] 44.4 g of thiacloprid

[0206] 5.6 g of β-cyfluthrin

[0207] 49.7 g of a mixture of alkylarylsulphonate, ethylhexanol andalkanol ethoxylate

[0208] 44.0 g of polyoxyethylene sorbitol oleate

[0209] 0.4 g of silicone oil and

[0210] 0.8 g of butylhydroxytoluene

[0211] are added with stirring at room temperature to a mixture of

[0212] 101.3 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2) and

[0213] 193.8 g of sunflower oil.

[0214] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 μm.

Example 8

[0215] For the preparation of a suspension concentrate

[0216] 121.0 g of thiacloprid

[0217] 15.2 g of β-cycluthrin

[0218] 78.6 g of a mixture of alkylarylsulphonate, ethylhexanol andalkanol ethoxylate

[0219] 60.0 g of polyoxyethylene sorbitol oleate

[0220] 0.6 g of silicone oil and

[0221] 1.2 g of butylhydroxytoluene

[0222] are added with stirring at room temperature to a mixture of

[0223] 120.0 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2) and

[0224] 203.4 g of sunflower oil.

[0225] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 μm.

Example 9

[0226] For the preparation of a suspension concentrate

[0227] 138.5 g of thiacloprid,

[0228] 60.0 g of polyoxyethylene sorbitol oleate

[0229] 12.0 g of polystyrene-acrylic acid copolymer

[0230] 48.0 g of polyoxyethylene fatty acid glyceride

[0231] 0.6 g of silicone oil and

[0232] 1.2 g of butylhydroxytoluene

[0233] are added with stirring at room temperature to a mixture of

[0234] 120.0 g of alkanol alkoxylate of the formula

R—O-(EO)₃—(PO)₆—H

[0235] in which

[0236] R represents alkyl having 12 to 14 carbon atoms,

[0237] EO represents —CH₂—CH₂—O,

[0238] PO represents

[0239] and the numbers 3 and 6 are average values, and

[0240] 219.7 g of rapeseed oil.

[0241] After addition is complete, the mixture is stirred at roomtemperature for a further 10 minutes. The homogeneous suspensionresulting in the course of this is firstly subjected to a coarsegrinding and then to a fine grinding so that a suspension is obtained inwhich 90% of the solid particles have a particle size of below 6 μm.

Use Examples Example I

[0242] Stability Test

[0243] For the determination of the stability, 100 g in each case of asuspension concentrate of the composition described in Example 2 arestored for a number of weeks at

[0244] −10° C.,

[0245] room temperature,

[0246] +30° C.,

[0247] +40° C.

[0248] +54° C.

[0249] alternating temperatures (6 hours at −15° C., then 6 hours at+30° C.).

[0250] The experimental results are compiled in the following tables.TABLE Ia Storage at −10° C. after 2 4 8 16 26 weeks weeks weeks weeksweeks Sediment vol-ume 99 in % *⁾ Sediment none Redispers-ability goodParticle size **⁾ in μm 5.35 Content of active 19.8 compound in %

[0251] TABLE Ib Storage at room temperature after 2 4 8 16 26 weeksweeks weeks weeks weeks Sediment volume in 97 89 % *⁾ Sediment none noneRedispers-ability good good Particle size **⁾ in μm 5.31 5.86 Content ofactive 20.1 19.6 com-pound in %

[0252] TABLE Ic Storage at +30° C. after 2 4 8 16 26 weeks weeks weeksweeks weeks Sediment volume in 94 84 % *⁾ Sediment none noneRedispers-ability good good Particle size **⁾ in μm 6.57 5.74 Content ofactive 20.0 19.8 com-pound in %

[0253] TABLE Id Storage at +40° C. after 2 4 8 16 26 weeks weeks weeksweeks weeks Sediment volume in 93 92 87 82 % *⁾ Sediment none none nonenone Redispers-ability good good good good Particle size **⁾ in μm 6.016.29 7.08 6.4 Content of active 20.2 19.3 20.1 19.7 com-pound in %

[0254] TABLE Ie Storage at +54° C. after 2 4 8 16 26 weeks weeks weeksweeks weeks Sediment volume 96 89 83 in % *⁾ Sediment none none noneRedispers-ability good good good Particle size **⁾ in μm 8.81 6.61Content of active 20.1 20.0 20.1 com-pound in %

[0255] TABLE If Storage at alternating temperatures after 2 4 8 16 26weeks weeks weeks weeks weeks Sediment volume 98 99 in % *⁾ Sedimentnone none Redispers-ability good good Particle size **⁾ in μm 5.62 6.17Content of active 20.0 19.8 com-pound in %

Example II

[0256] Penetration Test

[0257] In this test, the penetration of active compounds throughenzymatically isolated cuticles of apple tree leaves was measured.

[0258] Leaves were used which were cut off in the fully developed stateof apple trees of the variety Golden Delicious. The cuticles wereisolated by

[0259] firstly filling, by means of vacuum infiltration with a pectinasesolution (0.2 to 2% strength) buffered to a pH of between 3 and 4, leafdiscs which had been marked on the bottom with dye and punched out,

[0260] then adding sodium azide and

[0261] allowing the leaf discs treated in this way to stand until thedisintegration of the original leaf structure and the detachment of thenon-cellular cuticles.

[0262] After this, only the leaf cuticles of the tops of the leaveswhich were free from stomata and hairs were used further. They werewashed a number of times alternately with water and a buffer solution ofpH 7. The clean cuticles obtained were finally mounted on small Teflonplates and smoothed out and dried using a gentle jet of air.

[0263] In the next step, the cuticle membranes thus obtained were placedinto diffusion cells (=transport chambers) of stainless steel formembrane transport investigations. For this, using tweezers the cuticleswere placed centrally on the edges of the diffusion cells coated withsilicone grease and sealed using a likewise greased ring. Thearrangement had been chosen such that the morphological outer side ofthe cuticles was directed outwards, i.e. to the air, while the originalinner side was facing the interior of the diffusion cell. The diffusioncells were filled with water or with a mixture of water and solvent.

[0264] For determination of the penetration, 9 μl in each case of aspray liquor of the composition mentioned below was applied to the outerside of a cuticle.

[0265] Spray Liquor A

[0266] 0.2 g of thiacloprid

[0267] 0.4 g of sunflower oil

[0268] 0.4 g of formulating aids in 1 litre of water.

[0269] Spray Liquor B

[0270] 0.2 g of thiacloprid

[0271] 0.5 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2)

[0272] 0.3 g of formulating aids in 1 litre of water.

[0273] Spray Liquor C

[0274] 0.2 g of thiacloprid

[0275] 0.4 g of sunflower oil

[0276] 0.2 g of 2-ethyl-hexyl alkoxylate of the formula (Ic-2)

[0277] 0.2 g of formulating aids in 1 litre of water.

[0278] Spray Liquor D

[0279] 0.2 g of thiacloprid

[0280] 0.3 g of formulating aids in 1 litre of water,

[0281] (prepared from commercially available suspension concentrate bydiluting with water).

[0282] CIPAC water was in each case used in the spray liquors.

[0283] After the application of the spray liquors, the water was allowedto evaporate in each case, then the chambers were in each case turnedand placed in thermostatted baths, a saturated aqueous calcium nitrate4-hydrate solution in each case being located under the outer side ofthe cuticles. The penetration commencing therefore took place at arelative humidity of 56% and a set temperature of 25° C. Samples wereremoved at regular intervals using a syringe and investigated by meansof HPLC for the content of penetrated active compound.

[0284] The experimental results can be seen from the following table.The numbers stated are average values of 8 measurements. TABLE II Activecompound penetration in % after 5 h 10 h 20 h A 1  3  4 B 10  16 20 C 617 40 D  1

1. Oil-based suspension concentrates, consisting of at least oneagrochemical active compound which is solid at room temperature, atleast one penetration promoter, at least one vegetable oil, at least onenon-ionic surfactant or dispersing aid and/or at least one anionicsurfactant or dispersing aid and optionally one or more additives fromthe groups consisting of the emulsifying agents, the antifoam agents,the preservatives, the antioxidants, the colourants and/or the inertfilling materials.
 2. Suspension concentrates according to claim 1,characterized in that the agrochemical active compound contained is afungicide, bactericide, insecticide, acaricide, nematicide,molluscicide, herbicide, plant growth regulator, plant nutrient and/or arepellent.
 3. Suspension concentrates according to claim 1,characterized in that the agrochemical active compound contained isthiacloprid.
 4. Suspension concentrates according to claim 1,characterized in that the agrochemical active compounds contained arethiacloprid and β-cyfluthrin.
 5. Suspension concentrates according toclaim 1, characterized in that the penetration promoter contained is atleast one alkanol alkoxylate of the formula R—O-(-AO)_(m)H   (I) inwhich R represents straight-chain or branched alkyl having 4 to 20carbon atoms, AO represents an ethylene oxide radical, a propylene oxideradical, a butylene oxide radical or mixtures of ethylene oxide andpropylene oxide radicals or butylene oxide radicals and m representsnumbers from 2 to
 30. 6. Suspension concentrates according to claim 1,characterized in that the penetration promoter contained is2-ethyl-hexyl alkoxylate of the formula

in which EO represents —CH₂—CH₂—O—, PO represents

and the numbers 5 and 3 are average values.
 7. Suspension concentratesaccording to claim 1, characterized in that the vegetable oil containedis sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maizegerm oil, cottonseed oil and/or soya bean oil.
 8. Suspensionconcentrates according to claim 1, characterized in that the content ofagrochemical active compounds is between 5 and 30% by weight, ofpenetration promoter is between 5 and 55% by weight, of vegetable oil isbetween 15 and 55% by weight, of surfactants or dispersing aids isbetween 2.5 and 30% by weight and of additives is between 0 and 25% byweight.
 9. Process for the preparation of suspension concentratesaccording to claim 1, characterized in that at least one agrochemicalactive compound which is solid at room temperature, at least onepenetration promoter, at least one vegetable oil, at least one non-ionicsurfactant or dispersing aid and/or at least one anionic surfactant ordispersing aid and optionally one or more additives from the groupsconsisting of the emulsifying agents, the antifoam agents, thepreservatives, the antioxidants, the colourants and/or the inert fillingmaterials are mixed with one another and the resulting suspension isoptionally subsequently ground.
 10. Use of suspension concentratesaccording to claim 1 for the application of the agrochemical activecompounds contained to plants and/or their habitat.